Aluminum chloride-hydrocarbon polymerization catalyst fortification



INVENTOR.

ALUMINUM CHLORIDE April 27, 1954 Naf/:cm Fragen B IL.. mLiGQb o Patented Apr. 27, 1954 ALUMINUM CHLORIDE-HYDROCARBON POLYMERIZATION CATALYST FORTI- FICATIION Nathan Fragen, Whiting, Ind., assignor to Standard Oil Company,.Chicago, Ill., a corporation of Indiana YApplication February 27, 1951, SerialvNo. 212,966

' 4 Claims.

This invention relates to an improved method and means for polymerizing olens with an aluminum chloride hydrocarbon complex catalyst and it pertains more particularly to an improved process for obtaining largeyields of heavy polymer in the polymerization of mixed butylenes from-a butane-butylene refinery stream.

It has longrbeen known that normally gaseous olens can be converted to viscous liquid polymers by means of solid aluminum chloride as such or by means of liquid aluminum chloride double compounds or complexes. Effective use of an aluminum chloride hydrocarbon complex catalyst has been obtainedby passing dispersed liqueed olefins upwardly throughva cooled column thereof. An object of this invention-is to provide a further improvement in the use of aluminum chloridehydrocarbon complex in hydrocarbon conversion processes and particularly in processes for polymerizing normally gaseous olens such as propylene,` isobutylenes, normal butenes, and mixtures thereof. A particular object of the invention is to increase the quantity and quality of polymers obtainable in a given polymerization reactor by means of liquid aluminum chloride-hydrocarbon complex catalyst. Other yobjects will become apy parent as the detailed description of the invention proceeds. Y u n Briefly, the invention employs a .continuous liquid phase conversion systeml wherein liquid aluminum chloride-hydrocarbon complex catalyst is dispersed in a continuous liquidhydrocarbcn reactant phase,v the' continuous reactant phase with suspended liquid catalyst is rapidly impelled against coolingsurfacesto obtain a high l heat transfer coefcient and thus maintain asubstantially uniform temperature, the liquid cata- .lyst is continuously separated. from the hydrocarbon phase and the bulk of ii-is'recycledv and redispersed in the continuous .liquid -hydrocarbon but spaced .from the .bottom thereof, introducing liquid aluminum chloride,-hydrocarbon,Y complex y catalystat a level adjacentzfbut'spaced Yfrom the top of the reactor, stirring the hydrocarbon phase and suspended catalystinzthecentralportion of l light polymer.

should bein powder form of small particle size.

(Cl. 26m-683.15)

2 the reactor to impel it against peripheral cooling coils-or tubes through which a refrigerant is circulatedlto maintain a temperature in the range of about 0 F. to about 8 F. and preferably about 10 F. to 30 F., maintaining sufficient pressure to insure liquid phase conditions, e. g. about 50-100 p. s. i. g., withdrawing settled complex from a quiescent zoneat the bottom of the reactor and eiiluent product from the top thereof, discarding a minor part of the Withdrawn complex and recycling a major part of the withdrawn compleX for introduction into the upper part of the reactor at a rate which is greater than the charging stock feed rate, but less than 10- times the charging stock feed rate and which is preferably upwards of 2.5 times, but less than 7.5 times, the rate of charging stock introduction and continuously fortifying recycled catalyst by incorporating therewith (either outside or inside of the reactor) pounds per 1GO pounds of olefin in the charging stock. The reactor system and its method of operation is described and claimed in copending application Ser. No. 212,890 led February 27, 1951, and modifications and improvements, particularly with'respect to low temperature operations and relating to the nature and amount of the recycled catalyst stream as correlated with 30 the amount of make-up catalyst employed, operating temperature, etc., are described and claimed in copendingl application Ser. No. 212,917 filed v'February 27, 1951, the present invention being A directed to an improved method and means for supplying the make-.up aluminum chloride in sys- Y tems of this type. Y

, I have discovered that the method of preparing and introducing make-up aluminum chloride is of vital importance to the successful operation of the system. To avoid line plugging and catalyst handling difficulties, I prepare the make-up catalyst ras a `slurry (rather than as a complex) in The make-up aluminum chloride It should be suspended in dry light polymer (in the absence of added HC1) at ordinary temperature and the resulting slurry should be kept in turbulent state to avoid settling out of the powder. `'I'he slurry should be made continuously in small amounts and is preferably introduced into the ksystem as make-up catalyst within 2 minutes after its preparation. The use of light polymer as the slurrying agent also facilitates the subsequent flashing andstripping steps in that its recycle (as a make-up catalyst carrying agent) avoids foaming difficulties that might be encountered if the product stream consisted solely of heavy polymer. The term heavy polymer as employed herein means polymer having a viscosity greater than 50o seconds (Saybolt Universal) at 210 F., the S. S. U. viscosity of heavy polymer in lthe particular example hereinafter set forth being about 1000 seconds Saybolt Universal at 210 F. or 100 seconds Furol at 210 F. and being characterized by a ash point of at least 350 F. l

The invention will be more clearly understood from the following detailed description of a specic example read in conjunction with the accompanying drawing which forms a part of this specification and which is a schematic flow diagram of my improved process.

While the invention is applicable to liquid phase polymerization of normally gaseous olefins, such as propylene, isobutylene, normal butylenes, and mixtures thereof, it is primarily directed to the polymerization of a butane-butylene mixture-associated with butanes in so-called butano-butylene renery stream. In this example, the charging stock is a petroleum refinery butane-butylene stream containing about 26 weight per cent isobutylene; about 37 weight per cent normal butylenes, and about 36 weight per cent butanes, such stocks usually containing a small amount of propane, propylene, pentanes, and/or pentenes.

About 900 barrels per stream day of the butanebutylene charging stock from source l is caustic washed in wash system H with about .'74 gallon per minute of 10% aqueous NaOH. The wash solution is 'then dried by passage through calcium chloride driers in drying system l2. The dry charging stock is thencooled to a temperature of about 0 to 30 F. in one or more heat exchangers i3, the charging stock preferably being split at this time and one-third of it charged to eachof four continuous reactors so that the charge rate to each reactor will be about 520 gallons Aper hour.

Each of these reactors It is a cylindrical vessel about 121/2 feet high and 41/2 `feet inside diameter.

Just above the narrowed bottom portion of the reactor Vessel there is a baille plate I5 providedwith spaced openings, e. g. about eight` 4 inch holes. The base of the reactor is provided with two outlet conduits. Conduitv i6 preferably extends upwardly into a quiescent zone between plate i5 and the bottom of the reactor and it serves to discharge complex from the system. Conduit I1 communicates with the bottom of the reactor and serves as an inlet for pump' I8 which recycles liquid catalyst complex through line i9 to a point in the-reactor which is adjacent but spaced from the top thereof. Inthis particular example, catalyst complexis thusrecycled at the rate of about 2000 gallons per hour `While only about 2 to 20 gallons of complex is discharged through conduit l5.

At the upper part of the reactor, a Adoughnut baile 20 is provided with a central opening, to facilitate insertion of the Astirrer or impeller. The quiescent zone between baffle l20 and the top closure plate 2i provides a settling space for returning any entrained catalyst droplets to the reactor so that substantially catalyst free hydrocarbon product eiuent may be withdrawn through product discharge line 22. VThe product stream thus withdrawn from each reactor is.

then passed by line 2'8 to mixer 21 wherein itis*- fav 4 mixed with about 14 gallons per minute of aqueous caustic solution from source 2B. The mixture then passes to caustic settler 29 from which the caustic wash is Withdrawn through line 30 and the caustic washed product stream is intro- "duced byline 3l to lter tower 32-which may be a bed of sand, gravel, or preferably limestone (chat) for removing entrained aluminum compounds, particularly gelatinous aluminum hydroxide. The clear product stream then passes throughv heater 33 and is thence introduced into flash drum'34A which may operate at a pressure of about p. s. i. g. and a top temperature of kkabout 300F., albottom temperature of about vv32'0'F. being maintained by heater 35. In the flash tower, unreacted C4 hydrocarbons, chiefly butanes, are taken overhead through line 36, condensed in cooler 31 and collected in receiver From the base of the flash tower, a mixture of light-and heavy polymer passes by line 39 through-heater 40 to stripping tower 4I. Heater 40 raises the temperature of the polymer mixture vto'about 525" F. and careshould be taken to avoid'excessive-temperature at this point, a con- -ventional Dowtherm` boiler `usually being employed to supply heat exchange fluid in heater 40. It is also -u'sually desirable to add 110 pound steam from'f-line40' in amounts suflicient to facilitate the desired extent of stripping.

The stripper preferably operates at about atmospheric or reduced pressure, the stripping being effected vby pound steam introduced by lined-2, inert gas preferably being introduced by line`l13A at a lower point Vto insure removal of steam #duction through line 50 (about 110 to 150 gallons *per hour' -for the three-reactor system).

About to 180 gallons peihour of light polymer is recycled by line 5I to serve as a vehicle lfor vv introducing make-up aluminum chloride to the system. This recycled light polymer is dried 'in a calcium chloride drier f' 52 and then distributed into each of three mixers 53, each of -which` is connected by line-54 to its respective reactor` ltwith an outlet-in the reactor at substantiallythe same level as the outlet of complex recycleline I8. Aluminum chloride powder not larger than -20 mesh and preferably smaller than 40 mesh-is discharged from bin 55 (which is prefy e'rabl'y vibratedfby vibrator 56) in amounts regu- -lated by a screw feeder driven by motor 51 in to the-open topped mixer-53. Recycled and dried light' polymer is introduced into mixer 53 in amounts controlled by pump-58, the mixer preferably being provided with a motor driven stirrer Thus, approximately '.-1-to l, in this case about-'3, pounder-aluminum chloride is dispersed and slurried in each gallonr of recycled and dried vlight polymer and while the slurry remains tur- `bulerityit lis `forced by'pump 60 through line 54 into reactor I4. -In thisl particular example,

deliver abou't14 toone gallonpe'r minute. Thus,

*about40-to 60 gallons per hour of light polymer #containing 'about l0 tcp-'20 pounds per 4hour -of slurridfaluminum' chloride powdery is continuand wasteful.

'ously introduced into each of the'three reactors "to supply make-up catalyst for fortifying the recycled catalyst complex. This make-up aluminum chloride is thus supplied at a rate of about 0.4 to 0.8 weight per cent based on total charging 'stock or about 0.6 to 1.2 weight per cent based on total olefins charged. It has been found that smaller amounts of aluminum chloride employed 'in the manner and under the conditions described in this example produces a somewhat larger proportion of heavy polymer to light polymer, but fails to produce as much total conversion and as much total heavy polymer as I am able 'toproduce in my defined operation. Amounts of aluminum chloride of about 2.0 weight per cent based on total olefins charged is undesirable Thus, the amount of make-up aluminum chloride should be held Within the critically defined limits of about 0.6 to 1.2 Weight per cent based on total oleiins charged in this particular example.

As heretofore stated, aluminumV chloride-hydrocarbon complex catalyst is recycled from the base of the reactor to the upper portion thereof through line I9 at a rate of approximately 2000 gallons per hour. For effective catalyst usage and maximum conversion, this catalyst recycle vrate should be at least about 500 gallons per hour and it may be as high as 3000 to 4000 gallons per hour, the catalyst in all cases being fortified with the defined amounts of make-up aluminum chloride. The low temperatures are maintained in 'the reactor by circulating refrigerant through peripheral coils El in each reactor and eective heat transfer is attained by impelling the liquid phase hydrocarbon reactant suspended catalyst against these heat exchange surfaces by means of stirrer mechanism, which in this example consists of a motor driven shaft 62 carrying three discs 63 spaced about 2 feet apart on which radial impeller blades 64 are 'mounted about 45 degrees apart, each impeller blade being about 4 by 5 inches and their tip to tip distance on a diameter being about inches. The impeller shaft is rotated at a rate of about to 250, e. g. about f 100 R. P. M. This stirrer mechanism-serves the multiple function of obtaining a high heat transfer coefficient and simultaneously assuring intimate dispersion and contact of catalyst in the liquid hydrocarbon reactant phase. The aluminum chloride particles introduced as a slurry through line 54 quickly combine with the dispersed catalyst complex particles and thus fortify -the complex in situ. If desired, the make-up catalyst slurry may be introduced by line 54a into complex recycle line i9 instead of being introduced directly into the reactor.

It should be noted that the make-up aluminum chloride slurry is a relatively non-viscous suspension of powdered aluminum chloride and it is prepared at ordinary temperatures in the absence of added HC1 so that in the short time of `less than 2 minutes before the slurry enters the reactorit does not complex with the light polymer in which it is slurried, but on the contrary combines with the already formed complex to fortify it.

The temperature at which polymerization is not limited thereto.

vonly about 13% by volume based on total charging stock. At 45c F. conversion temperature with slightly less than .8 weight per cent make-up aluminum `chloride based on total olefins charged, 16 volume per cent of heavy polymer 'was obtainable based on total charge. At about 25 F. polymerization temperature and employing about .9 weight per cent make-up aluminum chloride, a 20 volume per cent yield of heavy polymer' was obtained based on total charge. In

all of these three examples, the total product polymer consisted of about 70% heavy polymer and 30% light polymer. It will thus be seen that for maximum polymer production, the conversion rtemperature should be below about 30 F. and the amount of make-up aluminum chloride should be at least about .5 weight per cent based on total olefins charged. Polymerization tem- -peratures may be even lower than 20 F. and

.be understood that the recited example is given by way of Yillustration and that my invention is The composition of the butano-butylene stream may be varied throughout a relatively wide range, although it is preferred that the mixed butylenes constitute about 20% to 80% of the total charge and that both isobutylene and normal butylene be present to the extent of at least about 10%. It is important in all cases that the hydrocarbon be in the continuous phase in the stirred portion of the reactor and in some cases it may be advantageous to recycle an aliquot portion of the total hydrocarbon reactor effluent with incoming charging stock. Alternative nishing and fractionation systems may be employed and it is desirable, for example, to introduce ammonia or ammonium hydroxide into the eliuent product stream prior to portions of the system wherein corrosion might otherwise be encountered, e. g. prior to mixer 21, prior toheater 33, etc.

The recycle of light polymer as a carrier for make-up aluminum chloride increases the ratio of light polymer to heavy polymer which passes through heater 33 into flash tower 34, into heater 40 and to stripper 4 l; this serves the useful function of avoiding foaming difficulties which might otherwise be encountered in the flash tower and stripper.

The polymers produced by my invention are of outstanding utility in many industrial elds and they are commercially marketed under the trade name Indopol.

I claim:

1. The method of adding make-up aluminum chloride to an olefin polymerization system employing aluminum chloride-hydrocarbon complex catalyst and producing heavy polymer having a viscosity greater than 500 seconds Saybolt Unversal at 210 F. and light polymer having a viscosity which is not greater than 500 seconds and which is substantially free from unpolymerized hydrocarbons, which method comprises avoiding complex formation of make-up aluminum chloride with slurrying agent in which it is added to the system by drying at least a part of the light polymer, continuously introducing dried light polymer into a mixing zone, separately metering into said mixing zone about .1 to 1 pound of powdered solid aluminum chloride smaller than 20 mesh per gallon of dried light polymer introduced thereto, effecting dispersion of the powdered aluminum chloride in the dry light polymer in the absence of both moisture andHCl and introducing the slurry into the polymerization system as make-up catalyst within about two minutes after its preparation While maintaining the powder suspended in the slurry by pumping it at a rapid rate.

2..In the process of polyinerizing normally gaseous oleiins containing at least 3 carbon atoms per molecule by introducing charging stock containing such oleins and also containing normally gaseous parafiinic hydrocarbons having at least 3 carbon atoms per molecule in liquid phase at a low level into a conversion zone which directly communicates at its base with a lower settling Zone and which communicates at its top with an upper settling zone, introducing aluminum chloride-hydrocarbon complex catalyst and make-up aluminum chloride into said conversion zone at a high level which is below the upper settling zone, at a rate which is in the range of about 1 to 10 times the charging stock feed rate, maintaining the temperature in the conversion zone in the range of about 0 to 80 F. by circulating a refrigerant through peripherally arranged heat exchangers, maintaining a con- `tinuous hydrocarbon phase in the conversion zone by withdrawing catalyst complex from the lower settling zone to prevent a complex interface from reaching the level of charging stock inlet, impelling the hydrocarbon phase containing dispersed liquid catalyst complex particles against said peripherally arranged heat eX- changers to obtain intimate contact between catalyst and hydrocarbon and simultaneously to keep exchanger surfaces clean and maintain uniform conversion temperature, withdrawing diluted reaction product from the upper settling zone and removing residual catalyst therefrom,

recycling a major portion of the catalyst complex removed from the lower settling zone for reintroduction at said high level in the conversion zone, discarding a minor amount of catalyst complex from the system and adding make-up aluminum chloride catalyst to the system to f compensate therefor, the improved method of operation which comprises removing normally gaseous hydrocarbons from the polymers produced in the conversion zone, separating the remaining polymers into a heavy polymer stream having a viscosity greater than 500 seconds Saybolt Universal at 210 F. and a light polymer stream of lower viscosity, drying at least a part of the light polymer, continuously introducing dried light polymer into a mixing zone, separately metering into said mixing Zone powdered aluminum chloride having a particle size smaller than 20 mesh, dispersing the powdered aluminum chloride in the dry light polymer in the absence of both moisture and HC1 to avoid complexing of the aluminum chloride with the light polymer and introducing the resulting slurry to provide said make-up aluminum chloride at said high level in said conversion zone within about two minutes after its preparation in amounts in the range of about 0.1 to 2,0 parts by weight of makeup aluminum chloride per part by weight of olenns charged to the conversion Zone.

3. The method of polymerizing isobutylene andnormal butenes which comprises introducing a dry liqueed stream consisting essentially of butanes, isobutylene and normal butenes and cooled to a temperature below 30 F. into a conversion Zone, separately introducing into said conversion zone a liquid aluminum chloride-hydrocarbon complex catalyst at a rate which is about 1 to l0 times the rate at which the charging stock is introduced thereto, intimately mixing the introduced liquid catalyst with the introduced liquid charging stock in the conversion zone while maintaining the introduced hydrocarb-ons as a continuous phase and mechanically impelling said hydrocarbons together with suspended catalyst complex against heat exchange surfaces for obtaining high heat transfer coc-ilicient and maintaining the conversion zone at a uniform temperature in the range of about 0 to 30 F., settling catalyst complex from the continuous hydrocarbon phase, recycling most of said settled complex to the reaction zone for resuspension therein, withdrawing diluted product from the reaction rione, removing residual catalyst from said product, then removing from said product unpolyinerized hydrocarbons originally introduced with the charging stock, then separating the product into a heavy fraction having a viscosity greater than 590 seconds Saybolt Universal at 210 F. and a light polymer of lower viscosity, drying at least a part of the light polymer, continuously introducing dried light polymer into a mixing zone, separately metering into said mixing zone powdered aluminum chloride smaller than 20 mesh in particle size, dispersing the powdered aluminum chloride in the light polymer in the absence of both moisture and HC1 and immediately pumping the slurry at a rapid rate into the conversion zone to supply an amount of make-up aluminum chloride therein in the range of 0.1 to 2.0 weight percent based on total olens lchar-ged to the conversion zone.

4. The method of claim 3 wherein the amount of make-up aluminum chloride introduced into the conversion zone is in the range of 0.6 to 1.2 weight percent based on oleins charged and wherein the slurry of make-up aluminum chloride in light polymer contains an amount oi powdered aluminum chloride in the range of 0.1 to l pound of aluminum chloride per gallon cf light polymer.

References Cited in the file of this patent UNITED STATES PATENTS Number 

1. THE METHOD OF ADDING MAKE-UP ALUMINUM CHLORIDE TO AN OLEFIN POLYMERIZATION SYSTEM EMPOLYING ALUMINUM CHLORIDE-HYDROCARBON COMPLEX CATALYST AND PRODUCING HEAVY POLYMER HAVING A VISCOSITY GREATER THAN 500 SECONDS SAYBOLT UNIVERSAL AT 210* F. AND LIGHT POLYMER HAVING A VISCOSITY WHICH IS NOT GREATER THAN 500 SECONDS AND WHICH IS SUBSTANTIALLY FREE FROM UNPOLYMERIZED HYDROCARBONS, WHICH METHOD COMPRISES AVOIDING COMPLEX FORMATION OF MAKE-UP ALUMINUM CHLORIDE WITH SLURRYING AGENT IN WHICH IT IS ADDED TO THE SYSTEM BY DRYING AT LEAST A PART OF THE LIGHT POLYMER, CONTINUOUSLY INTRODUCING DRIED LIGHT POLYMER INTO A MIXING ZONE, SEPARATELY METERING INTO SAID MIXING ZONE ABOUT .1 TO 1 POUND OF POWDERED SOLID ALUMINUM CHLORIDE SMALLER THAN 20 MESH PER GALLON OF DRIED LIGHT POLYMER INTRODUCED THERETO, EFFECTING DISPERSION OF THE POWDERED ALUMINUM CHLORIDE IN THE DRY LIGHT POLYMER IN THE ABSENCE OF BOTH MOISTURE AND HCI AND INTRODUCING THE SLURRY INTO THE POLYMERIZATION SYSTEM AS MAKE-UP CATALYST WITHIN ABOUT TWO MINUTES AFTER ITS PREPARATION WHILE MAINTAINING THE POWDER SUSPENDED IN THE SLURRY BY PUMPING IT AT A RAPID RATE. 